Alkene oxide polymerization

ABSTRACT

EPOXIDE COMPOUNDS ARE POLYMERIZED WITH A CATALYST COMPRISING (A) AN ORGANOMETALLIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF ORGANOALUMINUM AND ORGANOZINC COMPOUNDS AND (B) A METAL SALT OF A CARBOXYLIC ACID. THE RUBBERY HIGH MOLECULAR WEIGHT POLYMERS PRODUCED HAVE SUBSTANTIAL UTILITY IN THE AUTOMOBILE INDUSTRY FOR FABRICATING ARTICLES SUCH AS MOTOR MOUNTS, BODY MOUNTS, SUSPENSION SYSTEM PARTS, HOSES, TUBING, AND THE LIKE.

nited States Patent Oflice 3,737,419. Patented June 5, 1973 3,737,419ALKENE OXIDE POLYMERIZATION Henry L. Hsieh, Bartlesville, kla., assignorto Phillips Petroleum Company No Drawing. Filed June 7, 1965, Ser. No.462,122 Int. Cl. C08f 3/34, 7/12 US. Cl. 260--88.3 16 Claims ABSTRACT OFTHE DISCLOSURE Epoxide compounds are polymerized with a catalystcomprising (a) an organometallic compound selected from the groupconsisting of organoaluminum and organozinc compounds and (b) a metalsalt of a carboxylic acid. The rubbery high molecular weight polymersproduced have substantial utility in the automobile industry forfabricating articles such as motor mounts, body mounts, suspensionsystem parts, hoses, tubing, and the like.

This invention relates to alkene oxide polymerization. In one aspect,this invention relates to processes of polymerizing epoxides. In anotheraspect, this invention relates to catalyst systems for polymerizingalkene oxides.

The literature including the patent art describes a variety of differentprocesses for polymerizing alkene oxides to produce polymers. It hasbeen suggested that ethylene oxide and propylene oxide can bepolymerized in the presence of a metal salt of an organic acid. Ingeneral, this process results in the formation of a product which rangesin consistency from a liquid to a waxy solid. Other prior art processesof polymerizing alkene oxides involve the use of an organometalliccompound as a catalyst. Catalysts of this type have not met withcommercial success because of the extremely low monomer conversion rate.Moreover, the polymer products produced by means of the organometalliccatalyst range from liquids to high molecular weight waxy solids havingalmost no elastic properties.

According to this invention, these and other disadvantages of the priorart processes of polymerizing alkene oxides are overcome by means of anovel catalyst system comprising an organometallic compound and a metalsalt of an organic acid. The organometallic portion of the catalyst canbe an organozinc or an organoaluminum compound such as diorganozinccompounds, organozinc monohalides, organozinc monohydrides,triorganoaluminum compounds, organoaluminum monohalides, organoaluminummonohydrides, organoaluminum dihalides, organoaluminum dihydrides, andorganoaluminum sesquihalides. The above-identified compounds can beprepared by a variety of different processes well known in the art.

The metal salt of the organic acid in the novel catalyst of thisinvention is a carboxylate of a metal selected from Groups II-A, III-A,IV-A, II-B, VI-B, VII-B, and VIII of the Periodic Table of the Elementsreported in the Handbook of Chemistry and Physics, 45th Edition, pageB-2, The Chemical Rubber Company (1964). The metal salts used in thecatalyst can be prepared by different techniques well known in the art.For example, the desired metal in the form of the hydroxide can bereacted with the desired acid to form the corresponding metal salt.Since the actual technique employed for producing this portion of thecatalyst forms no part of the invention, its method of preparation mustnot be construed as limiting of the invention.

Accordingly, it is an object of this invention to provide an improvedprocess of polymerizing alkene oxides.

Another object of this invention is to provide a novel catalyst forpolymerizing alkene oxides.

A further object of this invention is to provide a process ofpolymerizing alkene oxides which results in the production of a rubberypolymer having good flexibility and elasticity.

Still another object of this invention is to provide a process ofpolymerizing alkene oxides which will result in the formation of apolymer product which is sulfur vulcanizable.

These and other objects of the invention will become apparent to oneskilled in the art after studying the following detailed description andthe appended claims.

The novel catalyst of this invention can be used for polymerizing anyalkene oxide to form a rubbery polymer having good flexibility andelasticity. For example, alkene oxides containing up to and including 20carbon atoms per molecule can be polymerized by the process of thisinvention. Generally, it is preferred that the alkene oxide monomercontain from about 2 to about 8 carbon atoms. Alkene oxides which can bepolymerized in accordance with this invention can be represented by theformula Bit-i041 wherein R and R' are selected from the group consistingof hydrogen, saturated aliphatic, saturated cycloaliphatic, monoolefinicaliphatic, diolefinic aliphatic (conjugated and non-conjugated),monoolefinic cycloaliphatic, diolefinic cycloaliphatic (conjugated andnon-conjugated), and aromatic radicals and combinations of these such asaralkyl, alkaryl, and the like. Some or all of the R and R radicals canbe halogen-substituted, and can contain oxygen in the form of an acyclicether linkage (O) or an oxirane group Further, the alkene oxidesrepresented by the above formula can contain 1 or 2 olefinic linkages, 1or 2 oxiranc groups, and up to 1 ether linkage. In addition, both Rvariables can represent a divalent aliphatic hydrocarbon radical which,together with the carbon atoms of the oxirane group, can form acycloaliphatic hydrocarbon nucleus containing from about 4 to about 10carbon atoms and preferably from about 4 to about 8 carbon atoms.

Specific examples of some of the alkene oxides which are within theabove structural formula and which can be homopolymerized orcopolymerized in accordance with this invention are ethylene oxide(epoxyethane); 1,2-epoxypropane (propylene oxide); 1,2-epoxybutane;2,3-epoxybutane; 1,2-epoxypentane; 2,3-epoxypentane; 1,2-epoxyhexane;3,4-epoxyhexane; 1,2-epoxyheptane; 2,3-epoxyoctane;2,3-dimethyl-2,3-epoxypentane; l,2-epoxy-4-methylpentane;2,3-epoxy-5-methylhexane; 1,2-epoxy-4,4-dimethylpentane;4,5-epoxyeicosane; 1-chloro-2,3-epoxypropane (epichlorohydrin);l-bromo-2,3-epoxypropane; 1,S-dichloro-Z,3-epoxypentane;2-iodo-3,4-epoxybutane; styrene oxide;

6-oxabicyclo [3 1 .0]hexane; 7-oxabicyclo[4.1.0]hepane;

3-propyl-7-oxabicyclo [4. 1.0]heptane; bis 2,3-epoxypropyl) ether;

tert-butyl 4,5epoxyhexyl ether; and 2-phenylethyl 3,4-epoxybutyl ether.

Unsaturated alkene oxides within the above structural formula, includingethers, which can be homopolymenzed or copolymerized with the saturatedalkene oxides include allyl 2,3-epoxypropyl ether (allyl glycidylether);

allyl 3,4-epoxybutyl ether;

l-methallyl 3,4-epoxyhexyl ether;

3-hexenyl 5,6-epoxyhexyl ether;

2,6-octadienyl 2,3,7,8'diepoxyoctyl ether;

6-phenyl-3-hexenyl 3-ethyl-5,6-epoxyhexyl ether;

3,4-epoxy-1-butene (butadiene monoxide);

3,4-epoxy-1-pentene;

-phenyl3,4-ep0xyl-pentene;

1,2,9,IO-diepoxy-S-decene;

6,7 -di-n-butyl-3 ,4,9',10-diepoxy-1,1 l-dodecadiene;

epoxy 'vinyl ether;

allyl 2-methyl-2,3-epoxypropyl ether;

3-cyclohexyl-2-propenyl 4-cyclohexyl-3,4-epoxybutyl ether;

2,4-pentadienyl 2,3-diethyl-3,4-epoxybutyl ether;

l-methallyl 6-phenyl-3,4-epoxyhexyl ether;

5- (4-tolyl)2,3-epoxypentyl vinyl ether;

bis[4-(3-cyclopentenyl)2,3-epoxybutyl] ether;

2-(2, 4-cyclohexadienyl)ethyl 2,3-epoxybutyl ether;

2-(2,5-cyclohexadienyl)ethyl 2-benzyl-4,5-epoxypentyl ether;

3,4-epoxy-1,5-hexadienyl isopropyl ether;

allyl 3,4-dimethyl-3,4-epoxyhexyl ether;

3,4-epoxy-4-(2,3-dimethylpheny1) l-butene;

3,4-dimethyl-3,4-epoxy-l-pentene;

5 4-methylcyclohexyl) 3 ,4-epoxy-1-pentene;

4,5-diethyl-4,5-epoxy-2,6-0etadiene;

4- (2,4-cyclopentadienyl) 1,2,6,7-diepoxyheptane; and

l-phenyl-1,2-epoxy-5,7-octadiene.

The catalyst of this invention comprises an organometallic compound anda metal salt of an organic acid. The catalyst can be prepared and usedby mixing the organometallic compound with the metal salt of the organicacid prior to or during the polymerization reaction. The organometallicportion of the catalyst can be represented by the formula wherein R" isa hydrocarbon radical selected from the group consisting of saturatedaliphatic, saturated cycloaliphatic, and aromatic containing from 1 to20 carbon atoms, inclusive, and combinations such as aralkyl, alkaryl,and the like; M is a metal selected from the group consisting ofaluminum and zinc; X is a member of the class consisting of hydrogen,fluorine, chlorine, bromine, and iodine; n is an integer of from 1 to 3,inclusive; m is an integer of from 0 to 2, inclusive; and the sum of theintegers n and m equals the valence of the metal M. Organozinc andorganoaluminum compounds Within the above formula include diorganozinccompounds, triorganoaluminum compounds, organozinc monohalides,organozinc monohydrides, organoaluminum monohalides, organoaluminumdihalides, organoaluminum sesquihalides, organoaluminum monohydrides,and organoaluminum dihydrides. 'Ihe organoaluminum sesquihalides asherein defined are intended to mean a mixture of organoaluminummonohalides and organoaluminum dihalides of the formulas R" AlX andR"AlX respectively, wherein R" is the same as hereinbefore defined withrespect to the general formula and X is a halogen. The organoaluminumsesquihalides can then be Written as R" Al X or as R" AlX Exemplaryorganometallic compounds within the above general formula includetrimethylaluminum; triethylaluminum;

tri-n-propylaluminum; triisobutylaluminum; tri-n-hexylaluminum;tri-n-octylaluminum; tricyclohexylaluminum; triphenylaluminum;tri-n-butylaluminum; tri-n-decylaluminum; tri-n-eicosylaluminum;methyldiphenylaluminum; tribenzylaluminum;bis(3,5-heptylpheny1)methylaluminum; tri-l-naphthylaluminum;di-n-octylphenylaluminum; tri-4-tolylaluminum; dimethylchloroaluminum;methyldichloroalurninum; methylisobutylchloroaluminurn;n-heptyldifiuoroaluminum; diphenylbromoaluminum; dibenzylchloroaluminum;di-n-octylchloroaluminum; n-octylphenylchloroaluminum;di-n-eicosyliodoaluminum; n-butyldihydroaluminum; methyldihydroaluminum;diisopropylhydroaluminum; ethylmethylhydroaluminum;diphenylhydroaluminum; benzyl-n-dodecylhydroaluminum; bis2,4,6-tri-n-butyloctyl) hydroaluminum; dimethylzinc;

diethylzinc;

di-n-propylzinc;

diisopropylzinc;

di-n-butylzinc;

diisobutylzinc;

di-n-amylzinc;

di-n-hexylzinc;

di-n-octylzinc;

di-n-dodecylzinc; dicyclopentylzinc; dicyclohexylzinc;bis(2,5-dimethyleyclopentyl)zinc; bis 3,5-dimethylcyclohexyl zinc;diphenylzinc; bis(2hexyltetradecyl)zinc; bis(4-cyclohexyloctyl)zinc;

his (Z-n-butylcyclohexyl Zinc;

bis (2,4,8-trimethylhendecyl )zinc; bis 7-pentyltetradecyl )zinc;

bis [2 (2,3,5-tri-n-butylphenyl)ethylJzinc; dibenzylzinc;

bis (4,6dicyclopentyldecyl)zinc; methylethylzjnc; ethylisopropylzinc;n-propyl-n-hexylzinc; methylchlorozinc; ethylbromozinc;n-propylchlorozinc; n-amylbromozinc; n-hexyliodozinc; n-octylchlorozinc;cyclopentylchlorozinc; cyclohexylbromozinc; 2-hexyltetradecylchlorozinc;7-pentyltetradecylbromozinc; benzylbromozinc;4,6-dicyclopentyldecylbromozinc; dodecylfluorozinc;3,S-methylcyclohexylchlorozinc; cyclohexyliodozinc; methylhydrozinc;cyclohexylhydrozinc; n-eicosylhydrozinc;

4-tolylhydrozinc; and n-amylhydrozinc.

The other component in the catalyst of this invention is a carboxylateof a metal selected from the group consisting of Groups I-I-A, III-A,IV-A, II-B, VI-B, VII-B, and VIII of the Periodic Table of the Elementsreported in the Handbook of Chemistry and Physics, 45th edition, pageB-2, The Chemical Rubber Company (1964). Preferred metals within theabove groups include beryllium, magnesium, calcium, strontium, barium,zinc cadmium, mercury, boron, aluminum, gallium, indium, thallium,silicon, germanium, tin, lead, chromium, molybdenum manganese, iron,cobalt, and nickel.

The organic acid which can be reacted or combined with the above metalscan be selected from the group consisting of monoand polycarboxylicaliphatic acids, monoand polycarboxylic cycloaliphatic acids, andmonoand polycarboxylic aromatic acids. It is preferred that the acid beselected from the group consisting of unsubstituted aliphatichydrocarbon mono, di-, and tricarboxylic acids containing from 1 to 30carbon atoms per molecule, inclusive; unsubstituted cycloaliphatichydrocarbon mono-, di-, and tricarboxylic acids containing up to andincluding 30 carbon atoms per molecule; and unsubstituted aromatichydrocarbon mono-, di-, and tricarboxylic acids containing up to andincluding three aromatic rings per molecule.

Exemplary saturated and unsaturated acids which are within this groupand which can be used in the practice of this invention include formic;acetic; propionic; butyric; caproic, capric; lauric; tridecanoic;stearic, palmitic; myristic; arachidic; behenic; tetracosanoic;triacontanoic; acrylic; maleic; crotonic; 3-butenoic; oleic; linoleic;linolenic; arachidonic; oxalic; malonic; succinic; sebacic, pimelic;1,2,3-propanetricarboxylic; 1,1,5 pentanetricarboxylic;1,2,4-hexanetricarboxylic; octene-2,3,6-tricarboxylic;cyclobutanecarboxylic; cyclopentanecarboxylic; 4methylcyclohexanecarboxylic;2,6-di-n-heptyl-4-n-nonylcyclohexanecarboxylic; 2,2,6trimethylcyclohexanecarboxylic; cyclopentylacetic;3-methylcyclopentylacetic; 2- cyclopentene-l-malonic; benzoic;Z-naphthoic or 2-naphthalenecarboxylic; 6,7diethyl-l-naphthalenecarboxylic; 1,4-naphthalenedicarboxylic;1,8-naphthalenedicarboxylic; 1 anthracenecarboxylic; 3phenanthrenecarboxylic; 1- phenanthrenebutyric; phthalic; terephthalic;1,2,3-benzenetricarboxylic; 1,3,5 benzenetricarboxylic; 1,4,6naphthalenetricarboxylic; 3-carboxycinnamic; 1 naphthaleneacrylic;cyclooctanecarboxylic acid; 1,5-cyclooctadiene-1- carboxylic acid;3-cyclohexene-l-carboxylic acid; 3-cyclohexene-l-carboxylic acid;l-cyclohexene-1,2-dicarboxylic acid; cyclotridecanecarboxylic acid;5-propyl-8,9,l2-tri-nbutylcyclotetradecanecarboxylic acid; andcyclopentadecanecarboxylic acid.

The monomer conversion rate can be increased by effecting thepolymerization in the presence of the novel catalyst system plus wateras a third component. In the practice of this modification of theprocess, the water can be employed in an amount within the range of fromabout 1 to about 100 gram millimoles per 100 grams of monomer andpreferably within the range of from about 5 to about 40 gram millimolesper 100 grams of monomer. It is obvious that lesser amounts of water canbe used if desired.

Although the amount of catalyst used for effecting polymerization of thealkene oxides can be varied over a rather broad range, it is preferredthat the organometallic component of the catalyst be present in anamount within the range of from about 1 to about 100 gram millimoles per100 grams of monomer and preferably within the range of from about 5 toabout 40 gram millimoles per 100 grams of monomer. The metal salt of theorganic acid can be present in an amount within a rather wide range. Forexample, the metal salt can be present in an amount within the range offrom about 0.3 to about 15 gram millimoles per 100 grams of monomer andpreferably within the range of from about 1.5 to about 8 gram millimolesper 100 grams of monomer. In the copolymerization of two or more alkeneoxide monomers, the amount of each of the components in the catalyst isbased on the total amount of all the monomers.

The alkene oxide polymerization reaction of this invention can becarried out either as a batch process or as a continuous process withthe novel catalyst system being added in a single initial charge or inpredetermined increments during polymerization. Similarly, the monomersmay be introduced into the reaction zone in one charge or they may beadded gradually during polymerization. In order to expedite and improvethe efiiciency of the polymerization reaction, it is generally preferredthat the reaction be carried out in the presence of an inert diluent.Suitable diluents which can be used for this purpose include parafiinc,cycloparafiinc, and aromatic hydrocarbons containing from about 4 toabout 10 carbon atoms per molecule. Exemplary diluents which can be usedare butane, pentane, hexane, decane, cyclopentane, cyclohexane,methylcyclohexane, benzene, toluene, xylene, ethylbenzene, and the like.It is also within the spirit and scope of this invention to employhalogenated hydrocarbons such as chlorobenzene and the like as diluents.Since the actual diluent employed is largely a matter of choice, it isobviously possible to employ other diluents than those herein identifiedwithout departing from the spirit and scope of the invention. Mixturesof suitable compounds can also be employed as diluents,

The temperature and pressure at which the polymerization process of thisinvention is effected can vary over a rather wide range. Generally, thepolymerization is conducted at a temperature within the range of fromabout 40 to about 250 F. and preferably within the range of from aboutto about 200 F. Polymerization is usually conducted at a pressure whichwill maintain the materials in the liquid state. It is obvious that thereaction can be conducted at superatmospheric pressures of severalthousand pounds if desired.

The duration of the polymerization reaction will depend primarily upontemperature, pressure, and catalyst activity. Usually, the process willbe conducted for a period of from a few minutes or less to about hoursor more.

The alkene oxide polymers and copolymers produced in accordance with thecatalyst system of this invention exhibit extremely good low temperatureflexibility. The polymers and copolymers are particularly resistant tothe effects of heat and to the effects of ozone. The alkene oxidepolymers have unlimited utility in the automobile industry forfabricating articles such as motor mounts, body mounts, suspensionsystem parts, hoses, tubing, and the like.

The following examples will serve to illustrate the operability of thecatalyst system of this invention. It is to be understood that suchexamples are for the purpose of illustration only, and that manyvariations and modifications can be made from the various exampleswithout departing from the concept of the invention.

EXAMPLES l-8 A series of runs was conducted whereby propylene oxide waspolymerized by means of the catalyst system of this invention. In theseveral runs made, the metal salt of the organic acid in the catalystsystem was varied to illustrate the operability of the invention withthe various groups of metals hereinbefore disclosed. Triisobutylaluminumwas used as the organometallic component in the catalyst. The materialswere charged to a reactor in the following proportions:

Propylene oxide, parts by weight 100 Toluene, parts by weight 860Triisobutylaluminum, mhm.* 30 Metal stearate, parts by weight 3Temperature, F. 158

Time, hours 48 Gram millimoles per 100 grams propylene oxide.

The actual polymerization technique employed involved the steps ofcharging the reactor with toluene and thereafter purging it withnitrogen. The metal salt of the stearic acid portion of the catalyst wasthen charged to the reactor followed by the propylene oxide and thetriisobutylaluminum. At the termination of each run, those reactionmixtures which were viscous were diluted with acetone to reduce theviscosity of the mass. Approximately one weight percent, based on thepolymer, of 2,2-methylene-bis(4-methyl-6-tert-butylphenol) antioxidantwas added. Each reaction mixture was then poured into water which hadbeen acidified with hydrochloric acid. This mixture was subsequentlyseparated into an aqueous phase and an organic phase. The organic phasewas removed and the polymer was recovered from it by evaporating thediluent. The recovered polymer was then dissolved in acetone andcoagulated in water for the purpose of removing residual amounts of themetal salt. The polymer products were then dried under vacuum. All ofthe polymers produced were rubbers. Those having the lower inherentviscosities were soft rubbers. Table I below illustrates the results ofeach of the runs and the properties of each of the rubber polymersproduced.

TABLE I Metal stearate Monomer conversion, Inherent Example No; TypeMhm. 1 percent viscosity 1 Mhm.=gram millimoles per 100 grams propyleneoxide.

In order to determine the inherent viscosity, one-tenth gram of polymerwas placed in a wire cage made from SO-mesh screen and the cage wasplaced in 100 ml. of toluene contained in a wide-mouth, 4-ounce bottle.After standing at room temperature (approximately 77 F.) for about 24hours, the cage was removed and the solution filtered through a sulfurabsorption tube of grade C porosity to remove any solid particlespresent. The resulting solution was run through a Medalia typeviscometer supported in a 77 F. bath. The viscometer was previouslycalibrated with toluene. The relative viscosity is the ratio of theviscosity of the polymer solution to that of toluene. The inherentviscosity is calculated by dividing the natural logarithm of therelative viscosity by the weight of the soluble portion of the originalsample.

A separate run was made with a catalyst comprising onlytriisobutylaluminum in accordance with the polymerization techniqueemployed in Examples 1-8. The polymer produced in this run was a liquidthus illustrating the important elfect of the metal salt of the organicacid in the catalyst system. Separate runs were also made using each ofthe metal stearates employed in Examples 1-8 as the sole catalyst inaccordance with the polymerization technique used in Examples 1-8. Onlya trace of liquid polymer was formed in each of the runs made. Thesecontrol runs show the unexpected result and the improved polymerobtained by utilizing both components of the catalyst.

EXAMPLES 9-16 A series of runs was made whereby propylene oxide waspolymerized by means of a catalyst comprising diethylaluminum chlorideand a metal salt of stearic acid. The metal in the salt of the stearicacid was changed to illustrate the operability of the catalyst withdifierent metals. The materials were charged to the reactor in the sameproportions and by the same technique as was employed in thepolymerization described in Examples 1-8 except that 30 millimoles ofdiethylaluminum chloride was substituted for the 30 millimoles oftriisobutylaluminum.

The reaction was conducted for a periodof 48 hours at a temperature of158 F. The results obtained from these examples are reflected in TableII below.

TABLE II Metal stearate Monomer conversion, Inherent Example No. TypeMhm. 1 percent viscosity Mhm.=grarn millimoles per 100 grams propyleneoxide.

The polymers produced by Examples 9-16 ranged from very soft to quitestilt rubbers. The polymers were recovered and inherent viscositydetermined for Examples 9-16 using the same technique as that describedin Examples 1-8.

Three runs were conducted whereby propylene oxide was polymerized in thepresence of water with the catalyst of this invention to illustrate theeifect obtained thereby. The materials were charged to the reactor inthe same proportions and by the same technique used in Examples 1-8. Inall three runs, 15 gram millimoles of water was added for each 100 gramsof monomer. The water was added to the reactor after thetriisobutylaluminum had been charged. The results obtained are presentedin Table III below.

l lllgfiiirriiMegi tarimillimoles per 100 grams propylene oxide.

It should be noted that Eaxmples 17, 18 and 19 are the same as Examples3, 6 and 7, respectively, except for the presence of the water duringpolymerization. It can be seen from these data that higher conversionsare obtained when water is employed in the catalyst. Further, thepolymers have a higher inherent viscosity when water is used. Theinherent viscosity and monomer conversion were determined in the samemanner as described in connection with Examples 1-8.

Two additional runs were made in the presence of a variable amount ofWater and a catalyst consisting only of triisobutylaluminum. These runswere made without a metal salt of an organic acid to illustrate thenecessity of the metal salt. The materials were charged to the reactorin the following proportions:

*Grams millimoles per 100 grams monomers.

The technique employed for charging the materials to the reactor was thesame as that employed and described in connection with Examples 1-8. Theresults obtained from these runs are reported in Table IV below.

TABLE IV Monomer Water, conversion Inherent Run N o mmoles (percent)viscosity l Gram millimoles per 100 grams monomer.

The polymer products produced in Runs 1 and 2 were both liquids. It isapparent from these data that a metal salt of an organic acid of theclass described is a necessary constituent in the catalyst in order toobtain a rubbery polymer. It can also be concluded from a comparison ofthe results in Examples 17-19 and the results in Runs 1 and 2 that themetal salt of the organic acid is a necessary component in the catalystwhen the polymerization reaction is effected in the presence of water.

As hereinbefore indicated, any unsaturated alkene oxide can behomopolymerized or copolymerized by means of the catalyst of thisinvention to form a rubbery polymer which can be sulfur vulcanized. Inthe copolymerization of propylene oxide and an unsaturated alkene oxide,it is preferred to employ allyl 2,3-epoxypropyl ether (allyl glycidylether) or 3,4-epoxy-1-butene (butadiene monoxide) in the formation ofthe copolymer. These copolymers are readily sulfur vulcanizable becausethe polymer chains contain a multiplicity of olefinic bonds.Polymerization conditions and techniques for copolymerizing two or morealkene oxides are the same as those employed in the homopolymerizationof alkene oxides. Thus, factors such as catalyst level, temperature,pressure, and the like in the homopolymerization reaction can beemployed in a like manner in the copolymerization reaction.

Although the invention has been described in considerable detail, itmust be understood that such detail is for the purpose of illustrationonly and that many variations and modifications can be made by oneskilled in the art without departing from the spirit and scope of theinvention.

I claim:

1. A process of producing a polymer of an epoxide compound whichcomprises polymerizing at least one alkene oxide of the formula whereineach R and each R is selected from the group consisting of hydrogen,saturated aliphatic, saturated cycloaliphatic, monoolefinic aliphatic,diolefinic aliphatic, monoolefinic cycloaliphatic, diolefiniccycloaliphatic, and aromatic radicals, halogen-substituted forms of saidradicals, and combinations thereof, and said radicals, theirhalogen-substituted forms and combined forms can contain oxygen in theform of an acyclic ether linkage (-O-) or an oxirane group I I .C. .C

and said alkene oxide can contain 1 or 2 olefinic linkages, 1 or 2oxirane groups, and 1 ether linkage, and both R radicals in said alkeneoxide can represent a divalent aliphatic hydrocarbon radical whichtogether with the oxirane group in said alkene oxide can form acycloaliphatic nucleus, said process comprising contacting said alkeneoxide with a catalyst comprising:

(a) an organozinc compound of the formula where in R" is a hydrocarbonradical selected from the group consisting of saturated aliphatic,saturated cycloaliphatic, and aromatic containing from 1 to 20 carbonatoms, inclusive; X is a member of the class consisting of hydrogen,fluorine, chlorine, bromine, and iodine; n is a number whose value is 1or 2; m is a number whose value is 0 or 1; and the sum of n and m equals2; said organozinc compound being present in an amount within the rangeof from about 1 to about 100 gram millimoles per 100 grams of monomer;and

(b) a salt of an acid selected from the group consisting of aliphaticacids, cycloaliphatic acids, and aromatic acids and a metal selectedfrom Groups II-A, III-A, IV-A, II-B, VI-B, VII-B and VIII of thePeriodic 10 Table; said salt of an acid being present in an amountwithin the range of from about 0.3 to about 15 gram millimoles per gramsof monomer.

2. A process according to claim 1 wherein said polymerization isconducted at a temperature within the range of from about 40 to about250 F.

3. A process according to claim 2 wherein said polymerization isconducted in the presence of water in an amount within the range of fromabout 1 to about 100 gram millimoles per 100 grams of alkene oxide.

4. A process according to claim 1 wherein said salt of an acid isselected from the group consisting of unsubstituted aliphatichydrocarbon acids containing from 1 to 30 carbon atoms, inclusive;unsubstituted cycloaliphatic hydrocarbon acids containing up to andincluding 30 carbon atoms; and unsubstituted aromatic hydrocarbon acidscontaining up to and including 3 aromatic rings and a metal selectedfrom Groups II-A, HI-A, -IV-A, II-B, VI-B, VII-B and VIII of theperiodic table.

5. A process according to claim 1 wherein said alkene oxide is propyleneoxide.

6. A process according to claim 2 for producing a copolymer of allylglycidyl ether and propylene oxide comprising contacting allyl glycidylether and propylene oxide at a temperature within the range of fromabout 40 to 250 F. with a catalyst comprising:

(a) an organozinc compound of the formula R",,ZnX wherein R" is ahydrocarbon radical selected from the group consisting of saturatedaliphatic, saturated cycloaliphatic, and aromatic containing from 1 to20 carbon atoms, inclusive; X is a member of the class consisting ofhydrogen, fluorine, chlorine, bromine, and iodine; n is a number whosevalue is 1 or 2; m is a number whose value is 0 or 1; and the sum of nand m equals 2; said organozinc compound being present in an amountwithin the range of from about 1 to about 100 gram millimoles per 100grams of allyl glycidyl ether and propylene oxide; and

(b) a salt of an acid selected from the group consisting of aliphaticacids, cycloaliphatic acids, and aromatic acids and a metal selectedfrom Groups I-I-A, IIIA, IV-A, II-B, VI-B, VII-B and VIII of theperiodic table, said salt being present in an amount within the range offrom about 0.3 to about 15 gram millimoles per 100 grams of allylglycidyl ether and propylene oxide, for a period of time suflicient tocopolymerize said allyl glycidyl ether and said propylone oxide; andrecovering the copolymer so produced.

7. A process according to claim 1 wherein said salt of an acid in thecatalyst system is a metal stearate.

8. A process according to claim 7 wherein the metal substituent isselected from the group comprising calcium, barium, zinc, iron,aluminum, cadmium, lead and magnesium.

5 A process of producing a polymer of an epoxide compound whichcomprises polymerizing at least one alkene oxide of the formula whereineach R and each R is selected from the group consisting of hydrogen,saturated aliphatic, saturated cycloaliphatic, monoolefinic aliphatic,diolefinic aliphatic, monoolefinic cycloaliphatic, diolefiniccycloaliphatic, and aromatic radicals, halogen-substituted forms of saidradicals, and combinations thereof, and said radicals, theirhalogen-substituted forms and combined forms can contain oxygen in theform of an acyclic ether linkage (-O) or an oxirane group and saidalkene oxide can contain 1 or 2 olefinic linkages,

1 1 1 or 2 oxirane groups, and 1 ether linkage, and both R radicals insaid alkene oxide can represent a divalent aliphatic hydrocarbon radicalwhich together with the oxirane group in said alkene oxide can form acycloaliphatic nucleus, said process comprising contacting said at leastone alkene oxide with a catalyst comprising:

(a) an organoaluminum compound of the formula R" AlX wherein R" is ahydrocarbon radical selected from the group consisting of saturatedaliphatic, saturated cycloaliphatic, and aromatic containing from 1 to20 carbon atoms, inclusive; X is a member selected from the groupconsisting of hydrogen, fiuorine, chlorine, bromine, and iodine; n is anumber whose value is 1, 2, or 3; m is a number whose value is 0, 1, or2; and the sum of n and m is 3; said organoaluminum compound beingpresent in an amount in the range of from about 1 to about 100 grammillimoles per 100 grams of monomer; and

(b) a salt of an acid selected from the group consisting of aliphaticacids, cycloaliphatic acids, and aromatic acids, and a metal selectedfrom Groups II-A, III-A, and IV-A of the periodic table; said salt of anacid being present in an amount within the range of from about 0.3 toabout 15 gram millimoles per 100 grams of monomer.

10. A process according to claim 9 wherein said polymerization isconducted at a temperature in the range of from about 40 to about 250 F.

11. A process according to claim 10 wherein said polymerization isconducted in the presence of water in an amount in the range of fromabout 1 to about 100 gram millimoles per 100 grams of monomer.

12. A process according to claim 10 wherein said acid component of saidacid salt is selected from the group consisting of unsubstitutedaliphatic hydrocarbon acids containing from 1 to 30 carbon atoms,inclusive; unsubstituted cycloaliphatic hydrocarbon acids containing upto and including 30 carbon atoms; and unsubstituted aromatic hydrocarbonacids containing up to and including 3 aromatic rings.

13. A process according to claim 9 wherein said alkene oxide ispropylene oxide.

14. A process according to claim 10 for polymerizing a mixture of allylglycidyl ether and propylene oxide.

15. A process according to claim 9 wherein said acid component of saidacid salt is stearic acid.

16. A process according to claim 15 wherein said metal component of saidacid salt is selected from the group consisting of calcium, barium,aluminum, lead, and magnesium.

References Cited UNITED STATES PATENTS 3,349,044 10/1967 Spitzer 260-2EPA HARRY WONG, JR., Primary Examiner US. Cl. X.R.

252431; 260-2 R, 2 EP, 2 A, 45.95, 79.5 C

